Low heat of hydration cement compositions and methods of using same

ABSTRACT

A method of servicing a wellbore in a subterranean formation, comprising preparing a cement composition comprising water and a cementitious material, wherein the cementitious material further comprises blast furnace slag, vitrified shale, calcium sulfate hemi-hydrate or combinations thereof, and placing the cement composition in the wellbore. A cement composition comprising water and a cementitious material, wherein the cementitious material further comprises blast furnace slag, vitrified shale, calcium sulfate hemi-hydrate or combinations thereof. A cement composition comprising water and a cementitious material, wherein the cementitious material further comprises blast furnace slag.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of and claims priority to U.S. patentapplication Ser. No. 13/450,110 filed on Apr. 18, 2012, which is adivisional of and claims priority to U.S. patent application Ser. No.11/385,426 filed on Mar. 21, 2006, published as U.S. 2007/0221379 A1,now U.S. Pat. No. 8,240,385 B2, and both entitled “Low Heat of HydrationCement Compositions and Methods of Using Same,” each of which is herebyincorporated herein by reference in its entirety. The subject matter ofthe present application is related to U.S. patent application Ser. No.11/385,416 filed on Mar. 21, 2006, published as U.S. 2007-0221378 A1,now U.S. Pat. No. 7,373,982, and entitled “Cements for Use AcrossFormations Containing Gas Hydrates,” which is hereby incorporated hereinby reference in its entirety for all purposes.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to servicing a wellbore. More specifically, itrelates to servicing a wellbore with cement compositions having a lowheat of hydration.

2. Background of the Invention

Natural resources such as gas, oil, and water residing in a subterraneanformation or zone are usually recovered by drilling a wellbore down tothe subterranean formation while circulating a drilling fluid in thewellbore. After terminating the circulation of the drilling fluid, astring of pipe, e.g., casing, is run in the wellbore. The drilling fluidis then usually circulated downward through the interior of the pipe andupward through the annulus, which is located between the exterior of thepipe and the walls of the wellbore. Next, primary cementing is typicallyperformed whereby a cement slurry is placed in the annulus and permittedto set into a hard mass (i.e., sheath) to thereby attach the string ofpipe to the walls of the wellbore and seal the annulus. Subsequentsecondary cementing operations may also be performed.

The completion of subterranean wellbores in fragile geographic zonessuch as in permafrost poses particular challenges. Permafrost is definedas soil that stays in a frozen state for more than two years. Cementcompositions for use for in subterranean formations within zones ofpermafrost must be designed to set before freezing and have a low heatof hydration. In addition to destabilizing the formation, high heats ofhydration promote the evolution of gas hydrates (e.g. methane hydrate)that are present in large amounts in permafrost. Gas hydrates, forexample methane hydrate, are metastable and can easily dissociate.

Thus there is an ongoing need for cement compositions having a low heatof hydration.

BRIEF SUMMARY OF SOME OF THE PREFERRED EMBODIMENTS

Disclosed herein is a method of servicing a wellbore in a subterraneanformation, comprising preparing a cement composition comprising waterand a cementitious material, wherein the cementitious material furthercomprises blast furnace slag, vitrified shale, calcium sulfatehemi-hydrate or combinations thereof, and placing the cement compositionin the wellbore.

Also disclosed herein is a cement composition comprising water and acementitious material, wherein the cementitious material furthercomprises blast furnace slag, vitrified shale, calcium sulfatehemi-hydrate or combinations thereof.

Further disclosed herein is a cement composition comprising water and acementitious material, wherein the cementitious material furthercomprises blast furnace slag.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter that form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand the specific embodiments disclosed may be readily utilized as abasis for modifying or designing other structures for carrying out thesame purposes of the present invention. It should also be realized bythose skilled in the art that such equivalent constructions do notdepart from the spirit and scope of the invention as set forth in theappended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Disclosed herein are cement compositions comprising water and acementitious material, wherein the cementitious material furthercomprises blast furnace slag, vitrified shale, calcium sulfatehemi-hydrate or combinations thereof. Further disclosed herein aremethods of preparing and using such compositions. Cement compositionscomprising blast furnace slag, vitrified shale, calcium sulfatehemi-hydrate or combinations thereof may also be referred to herein aslow heat of hydration cement compositions (LHCCs). The LHCCs disclosedherein may be employed in the servicing of a wellbore and mayadvantageously provide a low heat of hydration and high compressivestrength within a fragile geographic region such as permafrost and/orareas containing gas hydrates.

In an embodiment, the LHCC comprises calcium sulfate hemi-hydrate alsoknown as Plaster of Paris. Commercially available calcium sulfatehemi-hydrate also represented herein by the formula (CaSO₄.1/2(H₂O)), isa mixture of powdered and heat-treated gypsum which can be mixed withwater resulting in hardening of the plaster of paris to a smooth solidthat does not shrink or lose volume because it hardens before all thewater can evaporate. Calcium sulfate hemi-hydrate is widely availablecommercially from suppliers such as U.S. Gypsum and Georgia Pacific.

In an embodiment, calcium sulfate hemi-hydrate is present in the cementcomposition in an amount of from about 20% to about 80% by weight of drymaterial (bwod), alternatively from about 45% to about 75% bwod,alternatively from about 55% to about 65% bwod.

In an embodiment, the LHCC comprises blast furnace slag (BFS). BFSappears as the upper surface layer of molten iron released from a blastfurnace. The slag is separated from the iron and is considered aco-product of the production of iron and steel. BFS is a nonmetallicproduct consisting essentially of silicates, aluminosilicates ofcalcium, and other compounds that are developed in a molten conditionsimultaneously with the iron in the blast-furnace. BFS is widelyavailable commercially.

In an embodiment, BFS is present in the cement composition in an amountof from about 20% to about 80% bwod, alternatively from about 45% toabout 75% bwod, alternatively from about 55% to about 65% bwod.

In an embodiment, the LHCC comprises vitrified shale. Shale is afine-grained sedimentary rock whose original constituents were clays ormuds. It is characterized by thin laminae breaking with an irregularcurving fracture, often splintery, and parallel to the oftenindistinguishable bedding planes. The shale may then be subjected to theprocess of vitrification followed by being ground or milled to a desiredparticle size. Herein vitrification refers to heating of the material toa temperature that promotes the conversion of the shale into aglass-like amorphous solid which is free of any crystalline structure.In an embodiment, the vitrified shale is present in the cementcomposition in an amount of from about 35% to about 65% bwod,alternatively from about 40% to about 60% bwod, alternatively from about45% to about 55% bwod.

In an embodiment, the cementitious material of the LHCC comprises blastfurnace slag and calcium sulfate hemi-hydrate in a weight ratio of fromabout 1:4 to about 4:1; alternatively from about 2:3 to about 3:2;alternatively from about 0.45:0.55 to about 0.55:0.45. In an embodiment,the cementitious material of the LHCC comprises blast furnace slag andvitrified shell in a weight ratio of from about 1:4 to about 4:1;alternatively from about 2:3 to about 3:2; alternatively from about0.45:0.55 to about 0.55:0.45. In an embodiment, the cementitiousmaterial of the LHCC comprises vitrified shell and calcium sulfatehemi-hydrate in a weight ratio of from about 1:4 to about 4:1;alternatively from about 2:3 to about 3:2; alternatively from about0.45:0.55 to about 0.55:0.45.

In various embodiments, the cementitious material of the LHCC mayconsist or consist essentially of blast furnace slag, vitrified shale,calcium sulfate hemi-hydrate or combinations thereof. In variousembodiments, the cementitious material of the LHCC excludes materialamounts of hydraulic cement, for example a cement that includes calcium,aluminum, silicon, oxygen, and/or sulfur and which sets and hardens byreaction with the water. In various embodiments, the cementitiousmaterial of the LHCC excludes material amounts of Portland cements(e.g., classes A, C, G, and H Portland cements), pozzolana cements,gypsum cements, phosphate cements, high alumina content cements, silicacements, high alkalinity cements, or combinations thereof.

In an embodiment, the LHCC includes a sufficient amount of water to forma pumpable slurry. The water may be fresh water or salt water, e.g., anunsaturated aqueous salt solution or a saturated aqueous salt solution.Examples of salt solutions that may be used include without limitationbrine and seawater. The water may be present in an amount from about 20to about 180 percent by weight of cement, alternatively from about 28 toabout 60 percent by weight of cement.

In some embodiments, additives may be included in the LHCC for improvingor changing the properties thereof. Examples of such additives includebut are not limited to salts, accelerants, surfactants, set retarders,defoamers, settling prevention agents, weighting materials, dispersants,formation-conditioning agents, or combinations thereof. Other mechanicalproperty modifying additives, for example, are carbon fibers, glassfibers, metal fibers, minerals fibers, and the like which can be addedto further modify the mechanical properties. These additives may beincluded singularly or in combination. Methods for introducing theseadditives and their effective amounts are known to one of ordinary skillin the art.

In an embodiment, the LHCC comprises a density-reducing additive.Density-reducing additives such as hollow beads or foaming and expandingadditives such as foaming surfactants gas, suspension aids, defoamersand the like may be included in the LHCC to generate a lightweightcement slurry. In some embodiments, the choice of a density-reducingadditive may be dependent on the viscosity of the LHCC. In anembodiment, the LHCC is a foamed cement. Amounts of suchdensity-reducing additives and methods for their inclusion are known toone of ordinary skill in the art. As will by understood by one ofordinary skill in the art the inclusion of a density reducing additivesuch as foam into the LHCCs of this disclosure may display a reducedheat of hydration due to the reduced mass per unit volume. In variousembodiments, the LHCC may comprise a density greater than or equal toabout 10 lb/gallon.

In some embodiments, the LHCC may comprise a retarder. Herein a retarderrefers to a chemical additive used to increase the thickening time ofthe cement composition. The thickening time refers to the time requiredfor the cement composition to achieve 70 Bearden units of Consistency(Bc). At about 70 Bc, the slurry undergoes a conversion from a pumpablefluid state to a non-pumpable paste. Methods for the determination ofthickening time are outlined in API Specification 10B 22^(nd) Editiondated December 1997. Set retarders may be included by the user bymethods and in amounts known to one of ordinary skill in the art.Alternatively, such retarders may be part of the commercially availableformulations of other components of the disclosed LHCC. Withoutlimitation, an example of a set retarder is sodium citrate.

The components of the LHCC may be combined in any order desired by theuser to form a slurry that may then be placed into a wellbore. Thecomponents of the cement composition may be combined using any mixingdevice compatible with the composition, for example a bulk mixer. In anembodiment, the components of the LHCC are combined at the site of thewellbore. Alternatively, the components of the LHCC are combinedoff-site and then later used at the site of the wellbore. Methods forthe preparation of a LHCC slurry are known to one of ordinary skill inthe art.

In an embodiment, the LHCCs have a reduced heat of hydration whencompared to an otherwise identical composition comprising a Portlandcement. The heat of hydration of said compositions may be expressed asthe maximum temperature reached upon hydration T_(max). In anembodiment, 1800 grams of a LHCC has a T_(max) of from about 40° C. toabout 60° C. In an embodiment, the maximum heat evolved upon hydrationof the cement compositions of this disclosure is from about 10 btu/lb toabout 30 btu/lb.

In an embodiment, the LHCCs of this disclosure develop an appreciablecompressive strength in less than about 12:00 hours when placed into asubterranean formation. Herein the compressive strength is defined asthe capacity of a material to withstand axially directed pushing forces.The maximum resistance of a material to an axial force may be determinedin accordance with ASTM D 2664-95a. Beyond the limit of the compressivestrength, the material becomes irreversibly deformed and no longerprovides structural support and/or zonal isolation. In an embodiment,the LHCCs of this disclosure develop a compressive strength of fromabout 300 psi to about 500 psi, alternatively from about 1500 psi toabout 2000 psi.

The LHCCs disclosed herein can be used for any purpose. In anembodiment, the LHCC is used to service a wellbore that penetrates asubterranean formation. It is to be understood that “subterraneanformation” encompasses both areas below exposed earth and areas belowearth covered by water such as ocean or fresh water. In an embodiment, aLHCC is used to service a wellbore penetrating a fragile geographiczone, for example a wellbore in permafrost and/or a formation having gashydrates.

Servicing a wellbore includes, without limitation, positioning the LHCCdisclosed herein in the wellbore to isolate the subterranean formationfrom a portion of the wellbore; to support a conduit in the wellbore;and to seal an annulus between the wellbore and an expandable pipe orpipe string. The LHCC disclosed herein may withstand substantial amountsof pressure, e.g., the hydrostatic pressure of a drilling fluid orcement slurry, without being dislodged or extruded. Methods forintroducing compositions into a wellbore to seal subterranean zones aredescribed in U.S. Pat. Nos. 5,913,364; 6,167,967; and 6,258,757, each ofwhich is incorporated by reference herein in its entirety.

In an embodiment, the LHCCs disclosed herein may be employed in wellcompletion operations such as primary cementing operations. Saidcompositions may be placed into an annulus of the wellbore and allowedto set such that it isolates the subterranean formation from a differentportion of the wellbore. The LHCC thus forms a barrier that preventsfluids in that subterranean formation from migrating into othersubterranean formations. Within the annulus, the fluid also serves tosupport a conduit, e.g., casing, in the wellbore.

In other embodiments, additives are also pumped into the wellbore withthe LHCCs. For instance, fluid absorbing materials, particulatematerials, organophilic clay, resins, aqueous superabsorbers,viscosifying agents, suspending agents, dispersing agents, fluid lossagents, mechanical property modifying agents such as fibers, elastomersor combinations thereof can be pumped in the stream with thecompositions disclosed.

EXAMPLES

The invention having been generally described, the following examplesare given as particular embodiments of the invention and to demonstratethe practice and advantages thereof. It is understood that the examplesare given by way of illustration and are not intended to limit thespecification of the claims in any manner. In the following examples,heat of hydration measurements were recorded by placing a temperaturerecording thermocouple in an insulated silver-plated borosilicate glassvacuum flask and completely filling the flask with the slurrycomposition. Thickening time tests, compressive strength determinationsand rheology measurements were conducted in accordance with proceduresoutlined in API Specification 10.

Example 1

Several slurry compositions were prepared and the maximum temperaturerecorded during the setting process as shown in Table 1.

TABLE 1 Water/ Maximum Cement Temperature Run # Slurry Composition¹Ratio (° C.) 1 slag/hemi-hydrate 0.4 59 2 slag/hemi-hydrate + 0.1% Na0.4 59 citrate 3 slag/hemi-hydrate + 0.3% Na 0.4 58 citrate 4 sameslurry 22% foam quality 0.4 5 slag/hemi-hydrate + 0.5% Na 0.4  46²citrate 6 Class H cement/hemi-hydrate 0.38 79 7 Class H cement/Shale0.52 60 8 50/50 Class H cement/Pozzolonic + 0.57 84 2% Gel 9 Class Hcement/Slag 0.45 98 10 PERMAFROST low temperature 0.39 76 cement 11Class H cement 0.38 100  12 Class H cement + 5% Gel 0.44 100  13 Class Hcement + Lecithin 0.44 100  ¹All mixtures are 50/50 by weight with theexception of permafrost cement and 50/50 fly ash. ²At 27° C., Thickeningtime 5:47

Hereafter, calcium sulfate hemi-hydrate may be referred to forsimplicity as hemi-hydrate and blast furnace slag as slag. Na citrate isa set retarder that is widely commercially available. In Run 4, 22% foamquality refers to the introduction of foamed air that occupies 22% ofthe volume of the cement. Class H cement is an API designation referringto a class of Portland cement that may be used as a base cement from thesurface down to 8000 feet (2440 m), as it is or with accelerators orretarders to cover a wide range of depths and temperatures. Fly ash isthe residue from power plants which burn pulverized coal that can bemixed with lime to make a mortar that will also set under water. The gelis sodium bentonite, which is a water-swellable clay. PERMAFROST lowtemperature cement is a low heat of hydration cement commerciallyavailable from Halliburton Energy Services and is described in moredetail in U.S. Pat. Nos. 5,346,550 and 5,447,198 each of which areincorporated herein by reference in its entirety. The resultsdemonstrate that slurries containing blast furnace slag and calciumsulfate hemi-hydrate had the lowest heats of hydration.

Example 2

The compressive strength of several cement slurries was determined afterhaving set for 24 hours, Table 2. Also the difference between theinitial temperature of the slurry (approximately 27° C.) and the finalslurry temperature (ΔT) was recorded.

TABLE 2 Water/ Compressive Cement Strength Slurry Composition¹ Ratio(psi) ΔT (° C.)² Shale/Slag 0.55 253 — Shale/Cement 0.52 809 33Shale/Hemi-hydrate 0.52 425 — Hemi-hydrate/Cement 0.38 2000 52Hemi-hydrate/Slag 0.4 1690 29 Cement/Slag 0.45 2450 71 ¹All mixtures are50/50 by weight with the exception of permafrost cement and 50/50pozzolonic ²Difference between slurry temperature after mixing andmaximum temperature recorded during hydration.

Cement in Table 2 refers to Class H cement. The results demonstrate thata combination of slag and hemi-hydrate had the lowest ΔT, yet developeda compressive strength of 1690 psi after 24 hours at 140° F.

Example 3

A comparison of calcium sulfate hemi-hydrate from different sources wasmade to determine the effects, if any, on the cement composition. InTable 3a there is a comparison of the hydration properties for U.S.Gypsum (USG) hemi-hydrate to Georgia Pacific (GP) hemi-hydrate with a50/50 slag/hemi-hydrate and 40% water composition. Calcium sulfatehemi-hydrate from different sources contains a proprietary retarder. InTable 3b there is a comparison of the retarder response of USGhemi-hydrate and GP hemi-hydrate at 80° F. with a slurry composition of50/50 slag/hemi-hydrate, 0.5% sodium citrate and 40% water.

TABLE 3a Time to Maximum maximum Hemi- Temperature temperature hydrate(° C.) hours:minutes USG 60.1 4:55 GP 59.7 4:36

TABLE 3b Hemi- Thickening time hydrate hours:mins USG 10:22 GP  3:16

The results demonstrate that while the hemi-hydrate obtained fromdifferent sources (i.e U.S. Gypsum and Georgia Pacific) have similarhydration properties they have a dissimilar response to citrateretarder.

The concentration of set retarder, sodium citrate, was varied as shownin Table 4 for slurries having a 50/50 slag/hemi-hydrate and 40% watercomposition.

TABLE 4 Time to Maximum Sodium Citrate Heat Rise (g) ΔT (° C.)hours:minutes 0 29  3:50 1.6 30  5:30 4.8 29 10:20 8 17 31:30

The results demonstrate that increasing the sodium citrate concentrationdecreases the ΔT and increase the time to maximum heat rise.

Example 4

The effect of varying the water to cement ratio on the heat of hydrationwas determined as shown in Table 5 for a base slurry comprising 60:40USG hemi-hydrate:slag.

TABLE 5 Water to Maximum Temperature Cement Ratio Recorded (° C.) 0.4061.1 0.42 63.1 0.44 62.2

The results demonstrate that when the hemi-hydrate to slag ratio isfixed at 60:40, the water to cement ratio can vary from 0.40 to 0.44with no effect on the heat evolved.

Example 5

The compressive strength of three cement compositions having theindicated differing slag/hemi-hydrate ratios with 40% water weredetermined as shown in Table 6.

TABLE 6 Hemi-Hydrate/ Compressive Slag Ratio Strength (psi) 6/4 1950 5/51940 4/6 1750

The results demonstrate reasonable compressive strengths developed forthe various slag/hemi-hydrate ratios observed.

Example 6

The effect of a density-reducing additive on the heat of hydration wasdetermined, as shown in Table 7.

TABLE 7 Slurry Composition ΔT (° C.) 50/50 by weight Slag/Class H, 45%water 70.7 50/50 by weight Slag/Class H, 45% water 50.6 foamed to 11.35lb/gal Class H, 38% water 71.2 Class H, 38% water foamed to 11 lb/gal64.8 Class H, 38% water foamed to 8.6 lb/gal 53.3The results demonstrate that when the cement is foamed there is lesscement per unit volume and consequently less heat evolved while curing.

While preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the invention. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the inventiondisclosed herein are possible and are within the scope of the invention.Where numerical ranges or limitations are expressly stated, such expressranges or limitations should be understood to include iterative rangesor limitations of like magnitude falling within the expressly statedranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4,etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use of theterm “optionally” with respect to any element of a claim is intended tomean that the subject element is required, or alternatively, is notrequired. Both alternatives are intended to be within the scope of theclaim. Use of broader terms such as comprises, includes, having, etc.should be understood to provide support for narrower terms such asconsisting of, consisting essentially of, comprised substantially of,etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the preferred embodiments of the present invention.The discussion of a reference herein is not an admission that it isprior art to the present invention, especially any reference that mayhave a publication date after the priority date of this application. Thedisclosures of all patents, patent applications, and publications citedherein are hereby incorporated by reference, to the extent that theyprovide exemplary, procedural or other details supplementary to thoseset forth herein.

What is claimed is:
 1. A cement composition comprising water and acementitious material, wherein the cementitious material comprisesvitrified shale, wherein the cementitious material further comprisesblast furnace slag, calcium sulfate hemi-hydrate or combinationsthereof.
 2. The cement composition of claim 1 wherein the cementitiousmaterial comprises blast furnace slag and calcium sulfate hemi-hydratein a ratio of from about 1:4 to about 4:1.
 3. The cement composition ofclaim 1 wherein the cementitious material comprises blast furnace slagin an amount of from about 20% to about 80% by weight of dry material.4. The cement composition of claim 1 wherein the cementitious materialcomprises vitrified shale in an amount of from about 35% to about 65% byweight of dry material.
 5. The cement composition of claim 1 wherein thecementitious material comprises calcium sulfate hemi-hydrate in anamount of from about 20% to about 80% by weight of dry material.
 6. Thecement composition of claim 1 wherein the maximum heat evolved uponhydration of the cement composition is from about 10 btu/lb to about 30btu/lb.
 7. The cement composition of claim 1 wherein the cementcomposition has a compressive strength of from about 300 psi to about2000 psi upon curing.
 8. The cement composition of claim 1 furthercomprising a set retarder.
 9. The cement composition of claim 8 whereinthe set retarder comprises sodium citrate.
 10. The cement composition ofclaim 1 further comprising a density-reducing additive.
 11. The cementcomposition of claim 10 wherein the density-reducing additive comprisesglass beads, gas, or combinations thereof.
 12. The cement composition ofclaim 1 wherein 1800 grams of the cement composition has a T_(max) offrom about 40° C. to about 60° C.
 13. The cement composition of claim 7wherein the compressive strength develops in less than about 12 hours.14. The cement composition of claim 1 having a reduced heat of hydrationwhen compared to a similar cement composition comprising a hydrauliccement.
 15. The cement composition of claim 1 further comprising a fluidabsorbing material, a particulate material, an organophilic clay, aresin, an aqueous superabsorber, a viscosifying agent, a suspendingagent, a dispersing agent, a fluid loss agent, a mechanical propertymodifying agent, or combinations thereof.
 16. The cement composition ofclaim 1 substantially free of hydraulic cement.
 17. The cementcomposition of claim 1 substantially free of Portland cement.
 18. Thecement composition of claim 16 wherein the cement composition has acompressive strength of from about 300 psi to about 2000 psi in lessthan about 12 hours.
 19. The cement composition of claim 16 wherein 1800grams of the cement composition has a T_(max) of from about 40° C. toabout 60° C.
 20. The cement composition of claim 16 wherein the maximumheat evolved upon hydration of the cement composition is from about 10btu/lb to about 30 btu/lb.